Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients

Definitions

• the invention relates to liquid compositions that can form adherent, transparent, abrasion resistant polymeric films having prolonged antimicrobial properties.
• compositions intended for the controlled release of a disinfectant from a film of a stabilized hydrophilic polymer are disclosed in U.S. Pat. No. 3,966,902.
• the polymer complex is stabilized as a metal complex by the addition of an inorganic aluminum, zirconium or zinc salt such as aluminum chlorohydrol to the polymerization mixture.
• the stabilization adjuvant is necessary due to the fact that upon contact with water, films of simple hydrogels become highly swollen and rapidly elute their additives. Furthermore, dry films both simple and metal-complexed hydrogels do not adhere well to ceramic and other hard surfaces and lose their adhesion completely when wetted.
• the present invention provides liquid disinfectant compositions which yield adherent, water-resistant, polymeric films when coated onto porous or non-porous hard surfaces and dried.
• the liquid compositions comprise germicidal agents which are effective to destroy pre- existing microbial colonies and which impart prolonged antimicrobial properties to the deposited films.
• the liquid disinfectant compositions will comprise a film-forming copolymer of (a) a monomer having a hydrophilic group and (b) an alpha, beta-unsaturated carboxylic acid ester selected from the group consisting of aromatic esters, cycloalkyl esters and mixtures thereof.
• the copolymer will comprise about 20-99.5% of the hydrophilic monomer, and about 0.5-80 mol-% of the cycloalkyl or aromatic ester monomer, which can optionally be replaced with about 1-90% of an alkyl or alkoxy(alkyl) ester of an alpha, beta-unsaturated acid.
• the copolymers are substantially free of inorganic metal salt complexation agents such as those disclosed in U.S.
• copolymers can be viewed as modified hydrogels which are surprisingly capable of forming films which are adherent to hard surfaces and are resistant to removal when exposed to water and mild abrasion.
• the films can be readily deposited from dilute solutions or dispersions of the copolymer in volatile solvent systems.
• These liquid systems will also incorporate germicidal agents such as phenols or a quaternary ammonium salt. The agents are entrapped in the dried polymeric films, and can be incrementally released when the coated surface is contacted with moisture.
• the desirable properties of the present composition is due to the balance of hydrophilic and hydrophobic properties of the copolymer.
• the hydrophilicity of the resultant films may assist both the retention of the germicide and its exposure and activation by externally- applied water.
• the hydrophobicity imparted to the films by the aromatic and/or the cycloalkyl ester comonomer apparently imparts the necessary adherence and abrasion- resistance to the dried films.
• the term "prolonged” is intended to refer to the retention of substantial antimicrobial action as determined by laboratory test methods after at least 2 and most preferably after at least 5-10 water washes.
• volatile is intended to define solvents or solvent systems which readily evaporate when applied to hard surfaces in thin films at ambient conditions e.g. at about 15-35° C.
• the term "hard” is intended to refer to surfaces composed of refractory materials such as glazed and unglazed tile, brick, porcelain, ceramics, metals, glass and the like, and also includes hard plastics such as formica, polystyrenes, vinyls, acrylics, polyesters, and the like.
• Percentages of materials are weight percentages (wt-%) unless otherwise indicated.
• the liquid disinfectant composition of the present invention comprises a solution of a minor amount of a film-forming copolymer of (a) a monomer having a hydrophilic functional group, and (b) about 0.5-80 mol-% of said copolymer of an alpha, beta-unsaturated carboxylic acid ester selected from the group consisting of aromatic esters, cycloalkyl esters, and mixtures-thereof.
• the copolymer is dissolved in a major amount of a volatile solvent which also incorporates an amount of a germicidal agent effective to impart prolonged antimicrobial properties to the films formed upon removal of the solvent from coatings of said compositions.
• Copolymer monomer (b) preferably comprises a combination of a cycloalkyl ester or an aromatic ester of an alpha, beta-unsaturated acid in combination with about 1-90 mol-% of the cycloalkyl or aromatic ester of an alkyl ester or an (alkoxy)alkyl ester of an alpha, beta-unsaturated acid.
• Hydrophilic monomer materials which may be utilized in accord with the present invention are preferably esters of alpha, beta-unsaturated carboxylic acids such as methacrylic acid, acrylic acid, itaconic acid, aconitic acid, cinnamic acid, crotonic acid, mesaconic acid, carboxyethyl acrylic acid, maleic acid, fumaric acid and the like.
• preferred hydroxylalkyl esters include the esters of these acids and ethylene glycol, di-, tri-, tetra- and (poly)ethylene glycols, propylene glycol and dipropylene glycol; 1,3- or 1,4-butylene glycol; 1,6 hexamethylene glycol, and the like.
• the preferred unsaturated carboxylic acids include C 3 -C lo -carboxylic acids, i.e., acrylic acid, methacrylic acid, and itaconic acid.
• Suitable hydrophilic monomers containing amino groups as functional groups include the following: diethylaminoethyl acrylate or methacrylate, dimethylaminoethyl acrylate or methacrylate, monoethylaminoethyl acrylate or methacrylate, tert-butylaminoethyl methacrylate, piperidinoethyl methacrylate, morpholinoethyl methacrylate, dimethylaminopropyl acrylate and methacrylate, 2-pyrrolidinoethyl methacrylate, 3-dimethylaminoethyl-2-hydroxy-propyl acrylate or methacrylate, 2-aminoethyl acrylate or methacrylate, N - methyl acrylamide or methacrylamide, 2-hydroxyethyl acrylamide or methacrylamide, isopropyl-, t-butyl- and t-octylacrylamide or methacrylamide
• the film-forming copolymers of the present invention will incorporate about 20-99.5 mol-% of the hydrophilic monomer component, most preferably about 50-95 mol-%.
• the copolymerization of the hydrophilic monomer with at least one alpha, beta-unsaturated carboxylic acid ester selected from the group consisting of cycloalkyl esters, aromatic esters, and mixtures thereof substantially improves the adhesion of the copolymer films to hard surfaces.
• the copolymer will include about 0.5-80 mol-% of at least one of these modifying comonomers, most preferably about 1-50 mol-%.
• cycloalkyl ester includes bi- and tricycloalkyl esters, and the term “aromatic ester” includes hetero-aromatic esters.
• cycloalkyl and aromatic esters are those of acrylic acid, methacrylic acid or itaconic acid.
• Useful aromatic esters of these acids include phenyl, benzyl, tetrahydrofurfuryl, and phenoxyethyl esters.
• Useful cycloalkyl esters include C S -C 12 cycloalkyls, e.g. the cyclohexyl, isobornyl and adamantyl esters of these acids.
• Alkyl and alkoxy(alkyl) esters of alpha, beta-unsaturated carboxylic acids can be used in combination with the aromatic and/or cycloalkyl ester.
• the alkyl esters will be selected from higher(alkyl) esters, such as those of about 5-22 carbon atoms, most preferably about 5-12 carbon atoms.
• the alkyl and alkoxy (alkyl) esters can be employed to the extent of about 1-90 mol-% by weight of the total of the modifying comonomer.
• the mol-% ratio of cycloalkyl or aromatic ester to alkyl ester is about 2:1-1:2.
• alkyl and (alkoxy)alkyl esters of acrylic - acid, methacrylic acid and itaconic acid are preferred for use in the present comonomer mixtures.
• fatty-alkyl ester comonomers which can be employed in combination with cycloalkyl and/or aromatic ester monomers include myristyl, palmityl and stearyl acrylates, methacrylates and itaconates.
• C S -C 12 compounds examples include hexyl, octyl, ethyl(hexyl), isodecyl and lauryl, acrylates, methacrylates and itaconates.
• Alkyl esters having branched, as opposed to straight chain moieties are also preferred for use in the present copolymers.
• (Alkoxy)alkyl esters useful as comonomers include (C I -C 4 )alkoxy(C l -C 4 -alkyl) esters of acrylic, methacrylic or itaconic acid such as (methoxy)ethyl, (ethoxy)ethyl, (methoxy)propyl, (ethoxy)propyl and the like.
• the film-forming copolymers can be prepared by carrying out the polymerization of the monomers in a solvent or solvent mixture and at concentrations wherein the resultant copolymers remain in solution.
• Preferred solvents include lower alkanols such as ethanol; ketones, glycol esters or ethers, lower(alkyl)acetates; tetrahydrofuran, dimethylformamide and the like.
• the monomeric starting materials are typically dissolved in the solvent to the desired concentration, e.g. to a total concentration about 15-30% by weight, although higher or lower concentrations may be employed in some cases.
• the polymerization reactions are initiated in the conventional manner and preferably by use of radical-forming initiators.
• suitable initiators include dibenzoyl peroxide, tert-butyl peroctoate, cumene hydroperoxide, diazodiisobutyrodinitrile, diisopropylpercarbonate, ammonium persulfate, and the like, per se or in combination with a reducing agent, i.e., in the form of an oxidation-reduction system.
• the reaction mixture may be agitated and heated, preferably in a closed system under an inert atmosphere, to about 50-100°C, preferably to about 75-95°C.
• a solution of copolymer results, which can be employed without further purification or concentration in the present disinfectant compositions.
• the liquid compositions will incorporate an amount of one or more germicidal agents effective to both disinfect surfaces upon contact and to impart prolonged antimicrobial action to the polymeric films prepared therefrom.
• a wide variety of antimicrobial agents may be included in effective amounts without inducing undesirable interactions or chemical reactions between the major components of the compositions.
• Such agents can include chlorhexidine, chlorhexidine gluconate, glutaral, halazone, hexachlorophene, nitrofurazone, nitromersol, povidone-iodine, thimero- sol, C 1 -C 5 -parabens, hypochlorite salts, clofucarban, clorophene, poloxamer-iodine, phenolics, mafenide acetate, aminacrine hydrochloride, quaternary ammonium salts, oxychlorosene, metabromsalan, merbromin, dibromsalan, glyceryl laurate, sodium and/or zinc pyrithione, (dodecyl) (diethylenediamine)glycine and/or (dodecyl) (aminopropyl) glycine and the like.
• Phenolic compounds are among the preferred germicides for use in the present compositions.
• Useful phenolic germicides include phenol, m-cresol, o-cresol, p-cresol, o-phenyl-phenol, 4-chloro-m-cresol, chloroxylenol, 6-n-amyl-m-cresol, resorcinol, resorcinol monoacetate, p-tert-butyl-phenol and o-benzyl-p-chlorophenol.
• the biologically-active, water soluble salts of these compounds may also be employed, e.g., the alkali metal salts. Of these compounds o-benzyl-p-chlorophenol is preferred due to its high germidical power.
• Quaternary ammonium salts are also preferred germicides for use in the present invention and include the N-(higher) C 14 -C 24 -alkyl-N-benzyl-quaternary ammonium salts which comprise water solubilizing anions such as halide, e.g., chloride, bromide and iodide; sulfate, methosulfate and the like and the heterocyclic imides such as the imidazolinium salts.
• halide e.g., chloride, bromide and iodide
• sulfate, methosulfate and the like and the heterocyclic imides such as the imidazolinium salts.
• the aliphatiac quaternary ammonium salts may be structurally defined as follows: (R)(R 1 )(R 2 )(R 3 )N + X - wherein R is benzyl, or lower(alkyl) benzyl; R 1 is alkyl of 10 to 24, preferably 12 to 22 carbon atoms; R 2 is C 10 -C 24 -alkyl, Ci-C4-alkyl or Cl-C4-hydroxyalkyl, R 3 is lower alkyl or hydroxyalkyl of 1 to 4 carbon atoms and X represents an anion capable of imparting water solubility or dispersibility including the aforementioned chloride, bromide, iodide, sulfate and methosulfate.
• aliphatiac quats include n-C 12 -C 18 -alkyl-dimethylbenzylammonium chloride (myrisalkonium chloride), n-C 12 -C 24 -alkyl-dimethyl (ethylbenzyl) ammonium chloride (quaternium 14), dimethyl(benzyl)ammonium chloride and mixtures thereof.
• myrisalkonium chloride n-C 12 -C 24 -alkyl-dimethyl (ethylbenzyl) ammonium chloride (quaternium 14), dimethyl(benzyl)ammonium chloride and mixtures thereof.
• BTC 2125M is a mixture of myrisalkonium chloride and quaternium-14.
• N,N-di-(higher)-C 10 -C 24 -alkyl-N,N-di(lower)-C l -C 4 -alkyl-quaternary ammonium salts such as distearyl(dimethyl)ammonium chloride, cetyl(dimethyl)ethyl ammonium bromide, d.icoco(dimethyl)ammonium chloride, dihydrogenated tallow(dimethyl)ammonium chloride, di-tallow-(dimethyl)ammonium chloride, distearyl(dimethyl) ammonium methosulfate cetyl(trimethyl)ammonium bromide and di-hydrogenated-tallow(dimethyl)ammonium methosulfate.
• nitrogenous germicides include benzethonium chloride, cetylpyridinium chloride, methylben- zethonium chloride, domiphen bromide, gentian violet, and the like.
• the total concentration of the germicidal component of the present liquid compositions can vary widely, depending upon its antimicrobial activity, solubility, stability and the like. Although high weight ratios of germicide to copolymer, e.g. 2-3:1, can afford satisfactory disinfectant films, generally the concentration of the germicide will not exceed the concentration of the dissolved copolymer.
• the present disinfectant compositions will preferably comprise about 0.01-10%, most preferably about 0.05-5% by weight of the phenolic or quaternary ammonium salts.
• Highly durable, abrasion resistant films can be achieved when the total concentration of the germicidal agent in the present compositions comprises about 0.01-50%, preferably about 0.25-20%, and most preferably about 0.5-5% by weight of the dissolved copolymer.
• the present film-forming liquid compositions are readily prepared by dissolving the germicidal agent in a solution of the copolymer with agitation under ambient conditions, followed by dilution of the resultant solution to the appropriate concentration by addition of the volatile carrier solvent or solvent system.
• the copolymer is commonly prepared in a volatile solvent such as a lower(alkanol) or a lower(alkyl)acetate, this solution can be diluted with a compatible organic solvent.
• the organic solvent there can be employed alcohols, particularly lower aliphatic saturated alcohols, e.g. ethyl alcohol, isopropyl alcohol, propyl alcohol, glycols, e.g.
• ethylene glycol diethylene glycol, propylene glycol and dipropylene glycol ethylene glycol methyl ether, ethylene glycol ethyl ether, n-propylene glycol monomethyl ether, n-propylene glycol monoethyl ether, isopropylene glycol monomethyl ether, isopropylene glycol monoethyl ether, m-pyrol and ethyl acetate.
• Mixtures of these solvents with amounts of water can also be used, provided that the homogeneous solutions of the copolymer and the germicide are maintained.
• solutions formed by dissolving the germicide in ethanolic solutions of the comonomer can be diluted with a compatible volatile solvent or solvent system such as isopropanol (isopropyl alcohol) or isopropanol-water.
• a compatible volatile solvent or solvent system such as isopropanol (isopropyl alcohol) or isopropanol-water.
• Useful compositions of this type can comprise at least about 85% of a mixture of isopropanol and water.
• the preferred liquid disinfectant compositions of the present invention will comprise about 0.25-10%, preferably about 0.5-5% of the film-forming copolymer; about 0.10-10%, preferably about 0.05-5% of the germicidal agent, most preferably selected from a phenolic or quaternary ammonium salt; the remainder of the composition being the volatile solvent or solvent-system.
• the film-forming copolymer will incorporate about 50-95 mol-% of the hydrophilic monomer, most preferably 2-hydroxyethylmethacrylate or 2-hydroxyethylacrylate; and about 10-35 mol- % of a C 5 -C 8 -cycloalkyl acrylate or methacrylate, an aromatic acrylate or methacrylate or mixtures thereof.
• a higher(alkyl)acrylate or methacrylate monomer will also be included in the copolymer, replacing the cycloalkyl and/or aromatic monomer to the extent of about 25-75 mol-%.
• adjuvants such as an indicator of germicide level, fragrance, surfactants, dyes and the like may also be included in the present compositions, insofar as they are compatible with the film-forming process.
• adjuvants such as an indicator of germicide level, fragrance, surfactants, dyes and the like
• about 0.5-5% of a compatible surfactant can be included in the present compositions to enhance their cleaning power.
• the finished disinfectant compositions are homogeneous liquids which are applied to the surfaces to be treated by dipping, spraying, brushing, roller coating, pad coating or using similar coating procedures.
• hand-operated pump-type or pressurized aerosol sprayers are effective.
• the present compositions are particularly adapted to adhere to hard surfaces, they can also be employed to coat or otherwise treat materials such as sponges, flexible plastics, textiles, wood and the like.
• the coating process is continued to the extent required to deliver an amount of the liquid composition which rapidly dries to a clear, uniform polymeric film under ambient conditions, e.g., about 25-100 mg/in 2 of liquid composition is generally effective to disinfect and impart prolonged antimicrobial protection to tile surfaces.
• the germicidal films are glossy, resistant to mild abrasion and are not broken or substantially depleted of biocide by repeated wettings. Repeated application of the liquid compositions does'not result in film build-up since the solvents present can act to resolubilize and level the prior-applied film.
• a copolymer solution was prepared by the procedure of Example 1, with the exception that 3.0 mol-% cyclohexyl methacrylate, 7 mol-% isodecyl methacrylate and 90 mol-% 2-hydroxyethylmethacrylate were copolymerized.
• a copolymer solution was prepared by the procedure of Example 1, except that 7.0 mol-% cyclohexyl methacrylate, 3 mol-% isodecyl methacrylate and 90 mol-% 2-hydroxyethyl methacrylate were employed.
• Films of copolymers were cast from solutions prepared according to Examples 1-3 on glazed ceramic bathroom tiles and formica. After drying at ambient temperatures and humidities, the quality of the glossy films was tested. The appearance of the film and the abrasion caused by the application of a wet paper towel after the coated substrate had been immersed for 45 minutes in water were visually evaluated.
• copolymers containing the following hydrophobic cyclic and aliphatic methacrylates can be prepared:
• 5 to 50 mol-% of these monomers and/or combinations thereof within these molar limits can be polymerized with 95 to 50 mol% of hydrophilic comonomers such as 2-hydroxyethyl methacrylate, 2- or 3-hydroxy-propyl methacrylates and diacetone acrylamide.
• hydrophilic comonomers such as 2-hydroxyethyl methacrylate, 2- or 3-hydroxy-propyl methacrylates and diacetone acrylamide.
• Copolymer solutions prepared according to the procedure Example 1 which contained only 2-hydroxyethyl methacrylate and a single cycloalkyl, alkyl or aromatic methacrylate were prepared and their films on tiles and formica were evaluated by the procedures of Example 4.
• copolymers containing only a cycloalkyl or aromatic ester comonomer performed well on tiles but only weakly adhered to formica.
• Copolymers comprising C 11 -C 18 -alkyl comonomers exhibited satisfactory adhesion to formica but performed poorly on tiles.
• Copolymers comprising only a C 6 - or C l p-ester as the comonomer performed poorly in this evaluation.
• Solutions containing only polymerized hydrophilic monomers were prepared according to the procedure in Example 1, to evaluate the effect of eliminating other comonomers. Films were cast and their adhesion and abrasion resistance to glazed tiles and formica were evaluated after a 45 min. immersion in water.
• Two film-forming liquid disinfectant solutions were prepared by combining the copolymer solution of Example 1 with either a quaternary ammonium salt germicide ("quat" - a mixture of myristyl(dimethyl)(benzyl)ammonium chloride and dodecyl(dimethyl)(p-ethyl-benzyl) ammonium chloride, BTC 2125 M® - 80% active, Onyx Chemical C o., Jersey City, N.J., or a phenol (2-benzyl-4-chlorophenol) germicide, and isopropanol, as indicated on Table I V .
• quat a quaternary ammonium salt germicide
• BTC 2125 M® - 80% active Onyx Chemical C o., Jersey City, N.J.
• a phenol (2-benzyl-4-chlorophenol) germicide and isopropanol, as indicated on Table I V .
• Treated and untreated (control) tiles were inoculated with either E. coli or S. aureus (18-24 hr. broth cultures, 10 6 CFU/ml) and allowed to air dry.
• a one inch square sterile cloth swatch was moistened in sterile saline and employed to rub the tile surface in four back and forth motions. The cloth was placed into Letheen broth for enumeration of surviving organisms.
• the tiles were washed (sampled) daily for 14 days with reinoculation at days 5, 7 , 9 and 11. The results of this evaluation are summarized in Table VII.
• liquid disinfectant compositions were prepared by combining the individual components as summarized in Table VIII.
• Formulations I and II were evaluated as spray disinfectants on glass slides inoculated with s. aureus using a two minute exposure period by AOAC Method 4.033-4.035, AOAC Methods of Analysis (13th ed. 1980) at pages 63-64, the disclosure of which is incorporated by reference herein. All thirty inoculated slides sprayed with quat formulation I were negative for subsequent growth, as were 16 of 21 inoculated slides sprayed with phenolic formulation II. These results demonstrate that the film-forming liquid compositions of the present invention are effective to sanitize or substantially disinfect contaminated hard surfaces upon initial contact of the composition with the surface. As demonstrated by Example 7, the resultant films then act to impart prolonged residual antimicrobial properties to the treated surface, even after repeated water washes and microbial contamination.

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• Life Sciences & Earth Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Health & Medical Sciences (AREA)
• Dentistry (AREA)
• Zoology (AREA)
• Plant Pathology (AREA)
• Toxicology (AREA)
• Engineering & Computer Science (AREA)
• Agronomy & Crop Science (AREA)
• Wood Science & Technology (AREA)
• Pest Control & Pesticides (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Paints Or Removers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Materials For Medical Uses (AREA)

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Citations (3)

• 1986
  • 1986-02-14 NZ NZ215166A patent/NZ215166A/xx unknown
  • 1986-02-19 CA CA000502164A patent/CA1311682C/fr not_active Expired - Fee Related
  • 1986-02-21 AT AT86301236T patent/ATE65157T1/de not_active IP Right Cessation
  • 1986-02-21 EP EP86301236A patent/EP0194770B1/fr not_active Expired - Lifetime
  • 1986-02-21 DE DE8686301236T patent/DE3680219D1/de not_active Expired - Fee Related
  • 1986-03-11 NO NO860909A patent/NO860909L/no unknown
  • 1986-03-11 JP JP61051585A patent/JPS61233602A/ja active Pending
• 1991
  • 1991-10-11 SG SG851/91A patent/SG85191G/en unknown

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